Chemical Papers

DOI: 10.2478/s11696-013-0442-5

ORIGINAL PAPER

Synthesis, characterization and photoluminescence properties

of Ce3+ -doped ZnO-nanophosphors

Sudheesh K. Shukla, Eric S. Agorku, Hemant Mittal, Ajay K. Mishra*

Department of Applied Chemistry, University of Johannesburg P.O. Box 17011, Doornfontein 2028, Johannesburg, South Africa

Received 19 October 2012; Revised 31 March 2013; Accepted 15 May 2013

The present study involves the synthesis of Ce3+ doped ZnO nanophosphors by the zinc nitrate
and cerium nitrate co-precipitation method. The synthesized nanophosphors were characterized
with respect to their crystal structure, crystal morphology, particle size and photoluminescence
(PL) properties using X-ray diffraction (XRD), scanning electron microscopy (SEM)/energy disper-
sive X-ray (EDX), transmission electron microscopy (TEM)/ Energy-dispersive X-ray spectroscopy
(EDS) and PL-spectroscopy respectively. XRD results revealed that ZnO nanophosphors are single
phase and cubic type structures. Further, PL spectra of ZnO:Ce3+ nanophosphors showed green
emission because of the charge transfer at single occupied oxygen vacancies with ZnO holes and red
emission due to the cerium ion transitions. Intensity and fine structure of the Ce3+ luminescence
and its temperature dependence are strongly influenced by the doping conditions. The formation of
ZnO:Ce3+ nanophosphors was confirmed by Fourier transform infrared (FTIR) and XRD spectra.

c 2013 Institute of Chemistry, Slovak Academy of Sciences

Keywords: nanophosphors, doping, co-precipitation, FTIR, photoluminescence

Introduction et al., 2010). Luminescent materials, i.e. nanophos-

phors, emit radiation when stimulated with fast elec-
Due to their unique and fascinating properties, trons, X-rays, ultraviolet photons or some other form
nanostructured materials have triggered tremendous of radiation. In recent years, research has been boosted
motivation among scientists to explore their applica- by opto-electronic applications such as solid state
tions. Alkaline earth oxides gathered a lot of atten- lighting, lasers, displays and optical storage media and
tion in past decades because they are considered to medical diagnostic applications like biological assays.
be excellent host materials. Nanoparticles are a new Various types of materials can be used for nanophos-
group of advanced materials having different prop- phor production. They have bixbyte type oxide hosts
erties than bulk materials. These properties include with a cubic structure containing low symmetry sites
unique mechanical, chemical, physical, electrical, op- suitable for the incorporation of activators (rare earth
tical and surface area, which in turn define them as or transition metal ions) providing suitable emission
nanostructures. The most important characteristics of in the visible and near-infrared region.
the materials in the nano-size regime are their ability Zinc oxide (ZnO), particularly, exhibits attractive
to change their physical properties. During 1980s, a properties such as a wide direct band gap (3.37 eV)
considerable progress was achieved in the field of ma- (Hauschild et al., 2006; Klingshirn, 2007a; Jattaukul
terial science to understand the size related proper- et al., 2011), large excitation binding energy (60 meV),
ties in materials. When the size of the semiconductor low refractive index (1.9), resistance to high-energy
nanoparticles decreases, the energy gap (band gap) in- irradiation, stability to intense ultraviolet (UV) illu-
creases and the optical spectrum is shifted towards the mination and low toxicity (Cruz-Vázquez et al., 2005;
short wavelength region (Murray et al., 1993; Kumar Klingshirn, 2007b; Manam et al., 2009; Maciel et al.,

*Corresponding author, e-mail: [email protected]

ii S. K. Shukla et al./Chemical Papers

2010). ZnO nanoparticles are more versatile nanoma- ZnO nanophosphors and their source were: Zn(NO3 )2 ·
terials in biomedical applications due to their biocom- 6H2 O (Aldrich, USA, 99.9 mass %), ethanol (Merck,
patibility and high isoelectric point differences (∆IEP) Germany, 99 mass %), Ce(NO3 )3 · 6H2 O (Aldrich,
(Shukla et al., 2012). ZnO is a well suited semiconduc- USA, 99.9 mass %) and NaOH (Sigma–Aldrich, USA).
tor material with a variety of applications in the devel- All supplementary chemicals were of analytical grade
opment of UV optoelectronics because of its large ex- and used without further purification. All working
citation binding energy and versatile band gap (Kling- standards and aqueous solutions were freshly prepared
shirn et al., 2007). Moreover, ZnO is used in light with Millipore water (RO10TS) with the resistivity
emitting diodes (LED), lasers, field emission devices levels of more than 18.2 MΩ cm at 25 ◦C.
(FED), piezoelectric devices and chemical sensors due Spectroscopic studies of Ce3+ doped ZnO nano-
of its remarkable optical, electrical and photoelectrical phosphors were carried out with a Fourier transform
properties (Zimmler et al., 2009). infrared spectrophotometer (PerkinElmer Spectrum
Rare earth ions are widely used as activators in 100) and a photoluminescence (PerkinElmer LS 45
different hosts due to their high fluorescence efficien- fluorescence spectrometer with a Xe flash lamp) spec-
cies and very narrow line fluorescence bands. Rare trometer. Crystal phase of the synthesized nanophos-
earth doped nanophosphors are an attractive class of phors was determined by the X-ray powder diffraction
materials with optical emission from the 4f–4f or 4f– pattern taken on an X-ray diffractometer (Rigagu Ul-
5d transition of rare earth ions. The emission wave- tima IV) with CuKα (λ = 1.5405 Å) radiation. Par-
length depends strongly on the surrounding crystal’s ticle size and morphology of the synthesized Ce3+
field strength. Therefore, their emission can be tuned doped ZnO nanophosphors were determined on a scan-
by selecting an appropriate host lattice. Another at- ning electron microscope TESCAN (Vega 3 XMU)
tractive property of rare earth doped nanophosphors and the samples were fixed on the sample holder us-
is that they are photo-stable and their surface can ing carbon coating. TEM analysis of the samples was
be easily modified without altering their optical prop- performed using a field emission electron microscope
erties. This contribution introduces relatively simple (JEM-2100F). For TEM analysis, a drop of the syn-
nanophosphors’ design and processing. These charac- thesized Ce3+ doped zinc nanophosphors solution was
teristics make them suitable, for instance, for the use placed on the TEM carbon coated copper grid and
in the development of immunoassays, time resolved the film on the TEM grid was allowed to dry for a few
fluorescence imaging for quantitative histochemistry minutes after removing the extra solution using the
and DNA detection. Photoluminescence of cerium blotting paper and heat.
doped nanophosphors has been extensively studied be- Co-precipitation methods were used for the syn-
cause of the unusual interaction between the excited thesis of ZnO nanoparticles and Ce3+ doped ZnO
states and the host lattice. Typically, rare-earth ions nanophosphors. Initially, an aqueous solution of 1 M
emit from the well-shielded 4f orbitals and are there- Zn(NO3 )2 and 1 M NaOH were prepared by dissolv-
fore not significantly affected by the host lattice. How- ing each salt in double distilled water. The Zn(NO3 )2
ever, Ce3+ is different because there is only one elec- solution (10 mL) was heated upto 60 ◦C under con-
tron in the first shell of the 4f orbital (4f1 electronic stant stirring using a magnetic stirrer. Then, 1 M
configuration), and its luminescence transition (4f–5d) NaOH (10 mL) was added dropwise. The mixture was
can occupy only low symmetry sites in the matrix, i.e. centrifuged and the suspension was discarded. The
ZnO, and appears as distinct bands in the excitation precipitate was washed several times with absolute
spectra. Consequently, electrons are excited and emit ethanol and double distilled water. Ce3+ doped ZnO
from the high-energy 5d–orbitals. The relative energy was prepared in a similar manner; a calculated amount
of the 5d orbitals is highly dependent on the host lat- of Ce(NO3 )3 added to Zn(NO3 )2 and allowed to mix
tice. together homogeneously for 1 h under constant stir-
In the present study, cerium doped zinc phos- ring prior to the dropwise addition of NaOH. The pre-
phors (ZCNP) was synthesized by the co-precipitation cipitated slurry was kept in an oven at 100 ◦C for 12 h
method using Zn(NO3 )2 · 6H2 O and Ce(NO3 )3 · 6H2 O. to provide nanopowder Ce3+ doped ZnO nanophoh-
The synthesized ZCNP was characterized by Fourier phorus; finally, the obtained products were annealed
transform infrared (FT-IR) spectra, X-ray diffraction at 600 ◦C.
(XRD), scanning electron microscopy (SEM), energy–
dispersive X-ray (EDX) and transmission electron mi- Results and discussion
croscopy (TEM). Moreover, the luminescent property
was also studied using a photoluminescence (PL) spec- Fourier transform infrared spectroscopy
trophotometer.
Fig. 1 shows the FTIR spectrum of ZnO and
Materials and methods Ce3+ doped ZnO powder after calcination at 600 ◦C.
The bulk information on the IR spectra of ZnO
Starting materials for the synthesis of Ce3+ doped lies between 500 cm−1 and 400 cm−1 . The peak at
 S. K. Shukla et al./Chemical Papers iii

Fig. 1. FTIR spectra of ZnO:Ce3+ nanophosphors, Zn (–), Fig. 3. Energy level diagram showing the lowest energy ground
Zn:Ce3+ (–). state component and first excited states of Ce3+ in
nanophosphors. The cubic crystal field splitting is indi-
cated by ∆ and the non-cubic splitting by δ (Wu et al.
(2007); Ye et al. (2010)).

Fig. 2. Photoluminescence spectra of ZnO:Ce3+ nanophos-

phors, Zn (–), Zn:Ce3+ (–).
Fig. 4. XRD pattern of nanocrystalline ZnO:Ce3+ nanophos-
phors, Zn (–), Zn:Ce3+ (–).

530.93 cm−1 and 519.70 cm−1 were ascribed to ZnO

and Ce3+ doped ZnO respectively. The absorption
band at ≈ 3436 cm−1 was attributed to the O—H steps: i) excitation of the activator to a higher en-
stretching vibrations in both ZnO and Ce3+ doped ergy/excited state (10−11 s), ii) relaxation of the ac-
ZnO and originating from the surface OH groups. The tivator ion to the lowest energy level of the excited
peak at 1613 cm−1 is due to the first overtone of the state (10−8 s) and iii) emission of a lower-energy pho-
fundamental stretching mode of the O—H bond. The ton as the activator ion returns from its excited state
IR band between 519.70 cm−1 and 530.93 cm−1 can be to the ground state (10−9 s to 10−10 s) (Nalwa &
associated with oxygen deficiency and/or oxygen va- Rohwer, 2003). The Ce3+ ion is a well-known green-
cancy defect complex and ZnO (Kaschner et al., 2002). emitting activator in commercial nanophosphors im-
Changes of the oxygen composition can be evaluated proving their photoluminescence properties. Emis-
also indirectly considering the intensity of the spec- sions of Ce3+ are attributed to electronic transitions
troscopic band at ≈ 500 cm−1 because this vibration from the lowest excited state to the ground state and
is caused only by the oxygen sublattice (Xiong et al., they strongly depend on their local environments in
2006; Djelloul et al., 2010). the host lattice. The emission spectra of Ce3+ doped
ZnO nanoparticles were recorded by exciting the sam-
Photoluminescence analysis ple at the wavelength of 325 nm at room tempera-
ture (Fig. 2). The spectrum exhibits intense emission
Optical properties of the synthesized nanophos- peaks; one of them located at 392 nm (UV region)
phors were analyzed by photoluminescence spec- corresponding to the near gap band electronic emis-
troscopy. PL spectra of ZnO:Ce3+ involves three sion. A very broad emission spectrum was observed.
iv S. K. Shukla et al./Chemical Papers

Fig. 5. Scanning electron microscopy (SEM) of (A) Ce3+ undoped, (B) Ce3+ doped ZnO nanophosphor annealed at 600 ◦C; (C)
EDX curve of 3 atomic % Ce3+ doped ZnO nanophosphor.

The wide emission band is a result of the sum of emis- mation of a pure wurtzite structure of ZnO and the
sion peaks from 392 nm to 520 nm with a more in- imbedding of Ce3+ ions in the host crystal lattice.
tense peak appearing at 440 nm. The intense peak at The results obtained show that the Ce3+ ions par-
440 nm is a result of the emission from Ce3+ doped tially replaced the Zn2+ ions in the host material.
ZnO nanoparticles, which is due to the recombina- Diffraction peaks at the 2θ values of 31.84◦, 34.50◦,
tion of localized electrons at singly occupied oxygen 36.33◦, 47.65◦, 56.72◦, 63.01◦ and 68.11◦ correspond-
vacancies in deep trapped holes (van Dijken et al., ing to (100), (002), (101), (102), (110), (103) and
2000; Li et al., 2003). The intense peak at 550 nm (112) planes, respectively, were observed in the XRD
can be assigned to the 5 D0 –7 F0 transition. The PL pattern of ZCNP. XRD data indicate that the oxi-
bands at 392 nm and 440 nm are due to the cerium dized products are crystalline and single phase. The
ion transitions 2 D3/2 –2 F5/2 and 2 D3/2 –2 F7/2 , respec- mean particle size of ZCNP was calculated using the
tively (Fig. 3, Patra and Ganguli (1992); Reisfeld et Debye–Scherer’s equation (Kumaran & Gopalakrish-
al. (1999); Turos-Matysiak et al. (2006)). nan, 2012):
Kλ
XRD analysis D= (1)
β cos(θ)

Crystal phase of the nanophosphor was determined where D is the particle size, K is the constant (0.9), λ
by the X-ray powder diffraction pattern with CuKα is the wavelength of the X-ray radiation used (1.5405
(λ = 1.5405 Å) as shown in Fig. 4. Comparison of Å), β is the full width at half maxima (FWHM) in the
the recorded XRD patterns with the standard JCPDS radian of the (101) plane in the 2θ scale and θ is the
card number 36-1451 shows that synthesized ZnO and Bragg’s diffraction angle.
Ce3+ doped ZnO crystallites have wurtzite phase. No By fitting various peaks to this formula and tak-
other peaks were observed, which indicates the for- ing the instrumental broadening into account, values
 S. K. Shukla et al./Chemical Papers v

Fig. 6. Typical transmission electron microscopy (TEM) images of Ce3+ undoped (A), Ce3+ doped (B), single Ce3+ doped ZnO
nanophosphor (size = 46 nm) annealed at 600 ◦C (C), and EDS curve of 3 atomic % Ce3+ doped ZnO nanophosphor (D).

in the range from 29.70 nm to 50.15 nm with the error. According to the EDX data, 3 atomic % Ce3+
mean value of 31.6 nm were obtained for Ce3+ doped doping took place inside the zinc nanophosphors, sig-
ZnO. Moreover, the observed slight shift of the ma- nificantly influencing the red-luminescence behavior of
jor diffraction peaks towards a lower diffraction angle Ce3+ doped ZnO nanophophors.
with dramatic decrease of the intensity along with the
3 % atomic doping with Ce3+ ions resulted in a shift of Transmission electron microscopy
the oxygen position in the ZnO lattice. The observed
broadening factor was assigned to the decrease of the Typical TEM images of the Ce3+ doped ZnO
crystal size. nanophosphors are shown in Figs. 6A and 6B. These
images confirm the existence of a bulk quantity of
Scanning electron microscopy spherically shaped cerium doped zinc nanophosphors
bunches. Each of these bunches is closely packed at
Surface morphology of the synthesized Ce3+ doped the nanometer scale (Moghaddam et al., 2009). The
ZnO nanophosphor was examined by SEM as shown average particle size in the present case varies in the
in Figs. 5A and 5B, which reveal uniform distribution range of 30 nm to 51 nm with the mean value of
of the synthesized nanophophors over the surface of 32 nm. There is a good correlation between the val-
the ZCNP and good connectivity between the parti- ues obtained by mathematical calculation from an
cles. There is a well observable morphology difference XRD analysis and those obtained from TEM. The
between Ce3+ doped ZnO and ZnO alone. The EDX EDS studies (Fig. 6C) also confirmed the presence of
spectra (Fig. 5C) confirmed the presence of Ce3+ in 3 atomic % of Ce3+ ions in the cerium doped ZnO
the ZnO lattice; their atomic % being nearly equal to nanophosphors, significantly influencing their photo-
their nominal stoichiometry within the experimental luminescence properties.
vi S. K. Shukla et al./Chemical Papers

Conclusions Kumaran, S. M., & Gopalakrishnan, R. (2012). Structural, op-

tical and photoluminescence properties of Zn1−x Cex O (x =
Ce3+ doped ZnO nanophosphors were obtained by 0, 0.05 and 0.1) nanoparticles by sol–gel method annealed
under Ar atmosphere. Journal of Sol-Gel Science and Tech-
the co-precipitation method. FTIR studies clearly in- nology, 62, 193–200. DOI: 10.1007/s10971-012-2708-8.
dicated the presence of Ce3+ ions in cerium doped Li, Z. Q., Xiong, Y. J., & Xie, Y. (2003). Selected-control
ZnO nanophosphors. SEM and TEM analyses showed synthesis of ZnO nanowires and nanorods via a PEG-
the presence of the Ce3+ ion in the ZnO shell. The assisted route. Inorganic Chemistry, 42, 8105–8109. DOI:
particle size of Ce3+ doped ZnO nanophsophors varies 10.1021/ic034029q.
Maciel, A. V., da Nova Mussel, W., & Pasa, V. M. D.
in the range of 30 nm to 51 nm with the mean aver-
(2010). A novel synthesis of nanostructured ZnO via ther-
age value of 32 nm. Moreover, there is a good corre- mal oxidation of Zn nanowires obtained by a green route.
lation between the values obtained by mathematical Materials Sciences and Applications, 1, 279–284. DOI:
calculation from the XRD (Debye–Scherer’s equation) 10.4236/msa.2010.15041.
analysis and the results of the SEM and TEM studies. Manam, J., Das, S., & Isaac, A. (2009). Preparation, charac-
XRD results also showed that synthesized ZnO:Ce3+ terization and thermally stimulated luminescence of ZnO
nanophosphor. Indian Journal of Physics, 83, 1407–1419.
nanophosphor is crystalline with single phase. Photo- DOI: 10.1007/s12648-009-0129-5.
luminescence spectra showed a wide band from the Moghaddam, A. B., Nazari, T., Badraghi, J., & Kazemzad, M.
Ce3+ doped ZnO nanophophors confirming the pres- (2009). Synthesis of ZnO nanoparticles and electrodeposi-
ence of green emission peaks at 392 nm and 440 nm. tion of polypyrrole/ZnO nanocomposite films. International
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Murray, C. B., Norris, D. J., & Bawendi, M. G. (1993). Synthe-
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